Unusual photoluminescence properties of the 3D mixed-lanthanide–organic frameworks induced by dimeric structures: a theoretical and experimental approach

Rodrigues, Carime Vitória da Silva; Luz, Leonis Lourenço da; Dutra, José Diogo L.; Severino, Andrea; Malta, O.L.; Gatto, Claudia C.; Streit, Huayna Cerqueira; Freire, Ricardo O.; Wickleder, Claudia; Rodrigues, Marcelo O.

doi:10.1039/c4cp00405a

Cited by 29 publications

(13 citation statements)

References 51 publications

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“…The temperature‐dependent energy‐transfer rate constants k EnT of [EuTb(tmh) 6 (dpbp)] were also calculated by using the emission lifetimes of [Tb 2 (tmh) 6 (dpbp)] and [EuTb(tmh) 6 (dpbp)] (Supporting Information, Figure S12a) . Recently, Rodrigues and co‐workers calculated rate constants of energy transfer ( 5 D 4 → 5 D 0 and 5 D 4 → 5 D 1 ) using the multipolar and exchange mechanism . In our system, the relatively long distance between lanthanide ions in the crystal structure (min.…”

Section: Resultsmentioning

confidence: 97%

A Luminescent Dinuclear Eu^III/Tb^III Complex with LMCT Band as a Single‐Molecular Thermosensor

Yanagisawa

Kitagawa

Nakanishi

et al. 2018

Chemistry A European J

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Temperature-dependent luminescence of a dinuclear Eu /Tb complex with a seven-coordinate structure is demonstrated. The dinuclear complex is composed of two lanthanide ions, six tetramethylheptanedionate ligands, and a bidentate phosphine oxide linker ligand. The dinuclear structure of the complex was characterized by single-crystal XRD. Intrinsic 4f-4f emission quantum yields of the dinuclear Eu and Tb complexes were 66 and 61 %, respectively. The luminescence color of the dinuclear Eu /Tb complex changed from red to green with increasing temperature. The thermosensing range based on the ratio of luminescence intensity (A /A ) was 100-450 K. The temperature-dependent luminescence is due to the presence of a ligand-to-metal charge-transfer state.

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Section: Resultsmentioning

confidence: 97%

A Luminescent Dinuclear Eu^III/Tb^III Complex with LMCT Band as a Single‐Molecular Thermosensor

Yanagisawa

Kitagawa

Nakanishi

et al. 2018

Chemistry A European J

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“…The thermometric parameter Δ provides a reliable and robust method of determining the temperature, already used to map integrated circuits [ 15,29 ] and microfl uidic devices. [ 30 ] Figure 4 b presents the evolution of the integrated areas of the transitions depicted in Figure 4 dipole-quadrupole and quadrupole-quadrupole mechanisms, [ 31 ] is a clear signature of a two-step concerted temperature-assisted energy transfer, as reported for Eu 3+ /Tb 3+ co-doped di-ureasil organic-inorganic hybrids. [ 30 ] Further insight into the energytransfer mechanism is provided by the temperature dependence of the Δ parameter, which is well-described by the classical MottSeitz model for a single nonradiative recombination channel (see details in Figures S8 and S9, Supporting Information) [ 32 ] T…”

Section: C)mentioning

confidence: 99%

Lanthanide–Organic Framework Nanothermometers Prepared by Spray‐Drying

Wang

Ananias

Carné‐Sánchez

et al. 2015

Adv Funct Materials

262

181

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Accurate, noninvasive, and self-referenced temperature measurements at the submicrometer scale are of great interest, prompted by the ever-growing demands in the fi elds of nanotechnology and nanomedicine. The thermal dependence of the phosphor's luminescence provides high detection sensitivity and spatial resolution with short acquisition times in, e.g., biological fl uids, strong electromagnetic fi elds, and fast-moving objects. Here, it is shown that nanoparticles of [(Tb 0.914 Eu 0.086 ) 2 (PDA) 3 (H 2 O)]·2H 2 O (PDA = 1,4-phenylenediacetic acid), the fi rst lanthanide-organic framework prepared by the spray-drying method, are excellent nanothermometers operating in the solid state in the 10-325 K range (quantum yield of 0.25 at 370 nm, at room temperature). Intriguingly, this system is the most sensitive cryogenic nanothermometer reported so far, combining high sensitivity (up to 5.96 ± 0.04% K −1 at 25 K), reproducibility (in excess of 99%), and low-temperature uncertainty (0.02 K at 25 K).

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“…So far, in the first version of LUMPAC 31 and other articles 33 34 35 36 37 38 39 , the charge factors g i and polarizabilities α i are frequently adjusted in order to reproduce the experimental intensity parameters and . During the adjustment procedure, the calculated intensity parameters ( ) from the optimized geometry, obtained from one of our Sparkle Models, are compared with the experimental intensity parameters ( ).…”

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confidence: 99%

Europium Luminescence: Electronic Densities and Superdelocalizabilities for a Unique Adjustment of Theoretical Intensity Parameters

Dutra¹,

Lima²,

Freire³

et al. 2015

Sci Rep

Self Cite

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We advance the concept that the charge factors of the simple overlap model and the polarizabilities of Judd-Ofelt theory for the luminescence of europium complexes can be effectively and uniquely modeled by perturbation theory on the semiempirical electronic wave function of the complex. With only three adjustable constants, we introduce expressions that relate: (i) the charge factors to electronic densities, and (ii) the polarizabilities to superdelocalizabilities that we derived specifically for this purpose. The three constants are then adjusted iteratively until the calculated intensity parameters, corresponding to the 5D0→7F2 and 5D0→7F4 transitions, converge to the experimentally determined ones. This adjustment yields a single unique set of only three constants per complex and semiempirical model used. From these constants, we then define a binary outcome acceptance attribute for the adjustment, and show that when the adjustment is acceptable, the predicted geometry is, in average, closer to the experimental one. An important consequence is that the terms of the intensity parameters related to dynamic coupling and electric dipole mechanisms will be unique. Hence, the important energy transfer rates will also be unique, leading to a single predicted intensity parameter for the 5D0→7F6 transition.

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Unusual photoluminescence properties of the 3D mixed-lanthanide–organic frameworks induced by dimeric structures: a theoretical and experimental approach

Cited by 29 publications

References 51 publications

A Luminescent Dinuclear Eu^III/Tb^III Complex with LMCT Band as a Single‐Molecular Thermosensor

A Luminescent Dinuclear Eu^III/Tb^III Complex with LMCT Band as a Single‐Molecular Thermosensor

Lanthanide–Organic Framework Nanothermometers Prepared by Spray‐Drying

Europium Luminescence: Electronic Densities and Superdelocalizabilities for a Unique Adjustment of Theoretical Intensity Parameters

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Unusual photoluminescence properties of the 3D mixed-lanthanide–organic frameworks induced by dimeric structures: a theoretical and experimental approach

Cited by 29 publications

References 51 publications

A Luminescent Dinuclear EuIII/TbIII Complex with LMCT Band as a Single‐Molecular Thermosensor

A Luminescent Dinuclear EuIII/TbIII Complex with LMCT Band as a Single‐Molecular Thermosensor

Lanthanide–Organic Framework Nanothermometers Prepared by Spray‐Drying

Europium Luminescence: Electronic Densities and Superdelocalizabilities for a Unique Adjustment of Theoretical Intensity Parameters

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A Luminescent Dinuclear Eu^III/Tb^III Complex with LMCT Band as a Single‐Molecular Thermosensor

A Luminescent Dinuclear Eu^III/Tb^III Complex with LMCT Band as a Single‐Molecular Thermosensor